Identification of an Electrode-Adsorbed Intermediate in the Catalytic Hydrogen Evolution Mechanism of a Cobalt Dithiolene Complex

Analysis of a cobalt bis­(dithiolate) complex reported to mediate hydrogen evolution under electrocatalytic conditions in acetonitrile revealed that the cobalt complex transforms into an electrode-adsorbed film upon addition of acid prior to application of a potential. Subsequent application of a reducing potential to the film results in desorption of the film and regeneration of the molecular cobalt complex in solution, suggesting that the adsorbed species is an intermediate in catalytic H2 evolution. The electroanalytical techniques used to examine the pathway by which H2 is generated, as well as the methods used to probe the electrode-adsorbed species, are discussed. Tentative mechanisms for catalytic H2 evolution via an electrode-adsorbed intermediate are proposed.